Multilayer liquid crystal film, polarizing plate and method for preparing polarizing plate

ABSTRACT

The present specification provides a multi-layer liquid crystal film including: a substrate; a first alignment film comprising an alignment material and an acrylate in which a weight ratio of the alignment material to the acrylate is 3:1 to 5:1; a first liquid crystal film provided on the first alignment film; a second alignment film provided on the first liquid crystal film; and a second liquid crystal film provided on the second alignment film, and a method for manufacturing a polarizing plate, the method including: laminating the multi-layer liquid crystal film to a polarizer and peeling off the substrate.

The present application is a National Phase entry pursuant to 35 U.S.C.§ 371 of International Application No. PCT/KR2019/000897 filed on Jan.22, 2019 and claims priority to and the benefit of Korean PatentApplication No. 10-2018-0009456 filed in the Korean IntellectualProperty Office on Jan. 25, 2018, the entire contents of which areincorporated herein by reference.

FIELD

The present application relates to a multi-layer liquid crystal film, apolarizing plate, and a method for manufacturing a polarizing plate.

BACKGROUND

A retardation film may have various uses. The retardation film may bedisposed on one side or both sides of a liquid crystal cell, forexample, in order to improve viewing angle characteristics of a displaydevice. A retardation film is also used in order to prevent reflection,secure visibility, and the like in a reflective-type LCD or organiclight emitting device (OLED), or the like.

A retardation film may be manufactured, for example, by a liquid crystalmaterial. In order to use a liquid crystal material in a retardationfilm, the liquid crystal material may need to be appropriately alignedsuch that a desired retardation is exhibited. For example, in order tomanufacture a multi-layer liquid crystal film in which two or morealignment liquid crystal films are laminated, generally, there is amethod of laminating the respectively alignment liquid crystal filmsthrough an adhesive agent. However, this method has problems in that theprocess thereof is complicated, time-consuming, and expensive, and thefinal device has a large thickness.

Patent Document 1 relating to a method for manufacturing a multi-layerliquid crystal film without using an adhesive agent discloses coating arubbing-treated substrate with a vertical alignment liquid crystalmaterial by coating the rubbing-treated substrate with a horizontalalignment liquid crystal, and then adjusting the curing degree of thehorizontal alignment liquid crystal film. However, the manufacturingmethod of Patent Document 1 has a problem in that when the orientationof the vertical alignment liquid crystal is improved, the bondingstrength between liquid crystal films is reduced and the liquid crystalcoatability deteriorates, and a problem in that when the liquid crystalcoatability is improved, the alignability of the vertical alignmentliquid crystal deteriorates.

Further, a process of transferring a manufactured multi-layer liquidcrystal film to a polarizer, and then peeling off a substrate of themulti-layer liquid crystal film has been used in order to make apolarizing plate thinner, but when a substrate having a high peelingstrength between the substrate and a layer to which the substrate isattached is used, there is a problem in that a haze value is increasedafter peeling, and as a result, optical characteristics of a polarizingplate deteriorate, and when an additional transfer process is performed,the multi-layer liquid crystal film is not transferred to the polarizer.

(Patent Document 1) Korean Patent Application Laid-Open No. 2004-0002793

The present application provides a thinned multi-layer liquid crystalfilm, a method for manufacturing a polarizing plate by which it ispossible to obtain a polarizing plate having a low haze value after apeeling process because the peeling strength between a substrate and afirst alignment film is low, and a polarizing plate manufactured byusing the aforementioned process.

SUMMARY

An exemplary embodiment of the present invention provides a multi-layerliquid crystal film comprising: a substrate; a first alignment filmprovided on the substrate; a first liquid crystal film provided on thefirst alignment film; a second alignment film provided on the firstliquid crystal film; and a second liquid crystal film provided on thesecond alignment film,

in which the first alignment film comprises an alignment material and anacrylate, and

a weight ratio (of the alignment material to the acrylate is 3:1 to 5:1.

Another exemplary embodiment of the present invention provides apolarizing plate comprising: a polarizer; and the above-describedmulti-layer liquid crystal film provided on at least one surface of thepolarizer, in which the second liquid crystal film is disposed adjacentto the polarizer.

Still another exemplary embodiment of the present invention provides apolarizing plate comprising: a polarizer; a first alignment filmprovided on at least one surface of the polarizer; a first liquidcrystal film provided on the first alignment film; a second alignmentfilm provided on the first liquid crystal film; and a second liquidcrystal film provided on the second alignment film, in which the firstalignment film comprises an alignment material and an acrylate, and aweight ratio of the alignment material to the acrylate is 3:1 to 5:1.

Finally, an exemplary embodiment of the present invention provides amethod for manufacturing a polarizing plate, the method comprising:forming a first alignment film on a substrate by coating the substratewith a first alignment composition comprising an alignment material andan acrylate, in which a weight ratio (alignment material: acrylate) ofthe alignment material to the acrylate is 3:1 to 5:1; forming a firstliquid crystal film on the first alignment film; forming a secondalignment film on the first liquid crystal film; and forming a secondliquid crystal film on the second alignment film.

A multi-layer liquid crystal film of the present invention may not onlyachieve thinning of the liquid crystal film, but may also improve thecoatability of the liquid crystal without forming an adhesive agentbetween the liquid crystal film and an alignment film.

Further, the present invention may achieve thinning of a polarizingplate by laminating a multi-layer liquid crystal film to a polarizer,and then peeling off a substrate, and may obtain a polarizing plate, inwhich a peeling strength between the substrate and the first alignmentfilm is adjusted to 0.5 N or less by allowing a first alignment film tocomprise the alignment material and an acrylate such that a weight ratio(of the alignment material to the acrylate is 3:1 to 5:1, and a low hazevalue is obtained when the multi-layer liquid crystal film is laminatedto the polarizer, and then the substrate is peeled off.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic illustration of a stacking structure of amulti-layer liquid crystal film according to an exemplary embodiment ofthe present invention.

FIG. 2 is a schematic illustration of a process of manufacturing apolarizing plate according to an exemplary embodiment of the presentinvention.

FIG. 3 is a schematic illustration of a process of manufacturing apolarizing plate according to a further embodiment of the presentinvention. Index of reference numerals:

FIG. 4 is a schematic illustration of a stacking structure of amulti-layer liquid crystal film according to a further embodiment of thepresent invention.

1: Substrate

2: First alignment film

3: First liquid crystal film

4: Second alignment film

5: Second liquid crystal film

6: Polarizer

DETAILED DESCRIPTION

Hereinafter, exemplary embodiments of the present invention will bedescribed in more detail.

A multi-layer liquid crystal film according to an exemplary embodimentof the present application comprises: a substrate; a first alignmentfilm provided on the substrate; a first liquid crystal film provided onthe first alignment film; a second alignment film provided on the firstliquid crystal film; and a second liquid crystal film provided on thesecond alignment film, in which the first alignment film comprises analignment material and an acrylate, and a weight ratio (of the alignmentmaterial to the acrylate is 3:1 to 5:1.

The multi-layer liquid crystal film may have a thickness of 0.1 μm to 5μm excluding any substrate.

A horizontal alignment liquid crystal film may comprise a horizontalalignment liquid crystal material. A vertical alignment liquid crystalfilm may comprise a vertical alignment liquid crystal material.

In the present specification, a liquid crystal material may mean amaterial exhibiting liquid crystallinity. The liquid crystal materialmay comprise a site capable of exhibiting liquid crystallinity, forexample, a mesogen skeleton.

In the present specification, the horizontal alignment liquid crystalmaterial may mean a liquid crystal material capable of beinghorizontally alignment, and the vertical alignment liquid crystalmaterial may mean a liquid crystal material capable of being verticallyalignment.

In the present specification, the horizontal alignment may mean analignment state in which a director of a liquid crystal material isarranged in a state of having a tilt angle of about 0 to 5 degrees withrespect to the plane of a liquid crystal film.

In the present specification, the vertical alignment may mean analignment state in which a director of a liquid crystal material isarranged in a state of having a tilt angle of about 90 to 85 degreeswith respect to the plane of a liquid crystal film.

In the present specification, the director may mean an optical axis of aliquid crystal material. In the present specification, the optical axismay mean a slow axis of a liquid crystal material. As an example, whenthe liquid crystal material is in the form of a rod, the optical axismay mean a major axis of the liquid crystal material, and as anotherexample, when the liquid crystal material is in the form of disc(discotic), the optical axis may mean an axis in the normal linedirection of the disc.

In the present specification, the horizontal alignment may comprise aplanar alignment, a twist orientation, or a cholesteric alignment.

In the present specification, the planar alignment may mean an alignmentstate in which a liquid crystal material in a liquid crystal film ishorizontal alignment, and directors of the liquid crystal material forma layer in a state of being parallel to each other. The planar alignmentmay be referred to as having a uniform horizontal alignment.

In the present specification, the twist alignment or cholestericalignment may mean a spirally alignment state in which the liquidcrystal material in the liquid crystal film is aligned horizontally andthe directors of the liquid crystal materials form a layer while beingtwisted along the helical axis, and are aligned.

When a distance for a director of the liquid crystal material tocomplete a 360 degree rotation is referred to as a “pitch,” the liquidcrystal film in the twist alignment may have a thickness of less thanthe pitch. That is, in the liquid crystal film having the twistalignment, the director of the liquid crystal material may not berotated 360 degrees. In a liquid crystal film having the cholestericalignment, the director of the liquid crystal material may be rotated360 degrees. The cholesteric alignment has a spiral structure in whichthe directors of the liquid crystal compound form a layer while beingtwisted along the helical axis and are aligned, and the liquid crystalcompound may be rotated 360 degrees at the pitch.

The horizontal alignment liquid crystal material and/or the verticalalignment liquid crystal material may be a polymerizable liquid crystalmaterial. That is, the horizontal alignment liquid crystal materialand/or the vertical alignment liquid crystal material may comprise amesogen skeleton and one or more polymerizable functional groups. Thepolymerizable liquid crystal material may comprise, for example, one,two, three, or four or more of the functional groups. The polymerizablefunctional group may be an alkenyl group, an epoxy group, an acryloylgroup, a methacryloyl group, an acryloyloxy group, or a methacryloyloxygroup.

The horizontal alignment liquid crystal film may comprise the horizontalalignment liquid crystal material in a polymerized state. The verticalalignment liquid crystal film may comprise the vertical alignment liquidcrystal material in a polymerized state. In the present specification,“the liquid crystal material is included in a polymerized state” maymean a state in which the liquid crystal material is polymerized to forma skeleton such as a main chain or a side chain of the liquid crystalpolymer in the liquid crystal film.

As the horizontal alignment liquid crystal material or the verticalalignment liquid crystal material, polymerizable liquid crystalmaterials usually used in the art can be used without limitation.

In one example, the polymerizable liquid crystal material may be acompound represented by the following Formula 1.

In Formula 1, A is a single bond, —COO—, or —OCO—, R₁ to R₁₀ are thesame as or different from each other, and are each independentlyhydrogen, halogen, an alkyl group, a cycloalkyl group, an alkoxy group,an alkoxycarbonyl group, a cyano group, a nitro group, -U-Q-P, or asubstituent of the following Formula 2, or two adjacent substituents ofR₁ to R₅ or two adjacent substituents of R₆ to R₁₀ are linked to eachother to form a benzene substituted with -U-Q-P, provided that at leastone of R₁ to Rio is -U-Q-P or a substituent of the following Formula 2,or at least one pair of two adjacent substituents of R₁ to R₅ or twoadjacent substituents of R₆ to R₁₀ are linked to each other to form abenzene substituted with -U-Q-P, in which U is —O—, —COO—, or —OCO—, Qis an alkylene group or an alkylidene group, and P is an alkenyl group,an epoxy group, an acryloyl group, a methacryloyl group, an acryloyloxygroup, or a methacryloyloxy group.

In Formula 2, B is a single bond, —COO—, or —OCO—, R₁₁ to R₁₅ are thesame as or different from each other, and are each independentlyhydrogen, halogen, an alkyl group, a cycloalkyl group, an alkoxy group,a cyano group, a nitro group, or -U-Q-P, provided that at least one ofR₁₁ to R₁₅ is -U-Q-P, where U is —O—, —COO—, or —OCO—, Q is an alkylenegroup or an alkylidene group, P is an alkenyl group, an epoxy group, anacryloyl group, a methacryloyl group, an acryloyloxy group, or amethacryloyloxy group.

In Formula 2,

may mean that the moiety is linked to a mother compound. For example, inFormula 2,

on the left side of B may mean that B is directly linked to a benzene ofFormula 1.

The single bond may mean that no separate atom or atomic group ispresent at the corresponding site. For example, in Formulae 1 and 2, thesingle bond means a case where no separate atom is present at the moietyrepresented by A or B. More specifically, in Formula 1, when A is asingle bond, benzenes on both sides of A may be directly linked to forma biphenyl structure.

The alkylene group or alkylidene group may have 1 to 20 carbon atoms,and according to an example, the alkylene group or alkylidene group mayhave 1 to 16 carbon atoms, and according to another example, an alkylenegroup or alkylidene group having 1 to 12 carbon atoms, 1 to 8 carbonatoms, 1 to 4 carbon atoms, 4 to 10 carbon atoms, or 6 to 9 carbon atomsmay be exemplified. The alkylene group or alkylidene group may bestraight-chained, branch-chained, or cyclic.

The alkylene group or alkylidene group may be optionally substitutedwith one or more substituents.

The alkenyl group may have 2 to 20 carbon atoms, and according to anexample, the alkenyl group may have 2 to 16 carbon atoms, and accordingto another example, an alkenyl group having 2 to 12 carbon atoms, 2 to 8carbon atoms, 2 to 4 carbon atoms, 4 to 10 carbon atoms, or 6 to 9carbon atoms may be exemplified. The alkenyl group may bestraight-chained, branch-chained, or cyclic.

As an example of the alkenyl group, a vinyl group, an allyl group, apropenyl group, an isopropenyl group, a butenyl group, a hexenyl group,a cyclohexenyl group or an octenyl group, and the like may beexemplified, and the alkenyl group may be substituted with an additionalsubstituent.

In the present specification, the substituent which may be substitutedby any compound or substituent may be exemplified by halogen, a hydroxylgroup, an alkyl group, an alkoxy group, an alkenyl group, an epoxygroup, a cyano group, a carboxyl group, an isocyanate group, a mercaptogroup, an acryloyl group, a methacryloyl group, an acryloyloxy group, amethacryloyloxy group or an aryl group, and the like, but is not limitedthereto.

The aryl group may mean a monovalent residue derived from a compoundhaving a benzene ring or comprising a structure in which two or morebenzene rings are condensed, or a derivative thereof. Furthermore, thearyl group may be a concept comprising an aralkyl group and the like.The aryl group may have 6 to 22 carbon atoms, and may have 6 to 16carbon atoms according to an example.

As an example of the aryl group, a phenyl group, a phenylethyl group, aphenylpropyl group, a benzyl group, a tolyl group, a xylyl group, or anaphthyl group, and the like may be exemplified, and the aryl group maybe substituted with an additional substituent.

According to an exemplary embodiment of the present invention, P′s inFormulae 1 and 2 may be each independently an acryloyl group, amethacryloyl group, an acryloyloxy group, or a methacryloyloxy group.Further, in another example, P′s in Formulae 1 and 2 may be eachindependently an acryloyloxy group or a methacryloyloxy group.

In Formulae 1 and 2, a substituent which is not 7substituted with -U-Q-Por Formula 2, in which at least one may be present may be bonded to oneor more positions of R₃, R₈, and R₁₃.

According to an exemplary embodiment of the present invention, inFormulae 1 and 2, a substituent which is not substituted with -U-Q-P orFormula 2 may be hydrogen, halogen, a straight-chained or branched alkylgroup having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 12carbon atoms, a cyano group, an alkoxy group having 1 to 4 carbon atoms,or a nitro group.

In another exemplary embodiment, in Formulae 1 and 2, a substituentwhich is not substituted with -U-Q-P or Formula 2 may be chlorine, astraight-chained or branched alkyl group having 1 to 4 carbon atoms, acycloalkyl group having 4 to 12 carbon atoms, an alkoxy group having 1to 4 carbon atoms, or a cyano group.

In one example, as the horizontal alignment material, a compound inwhich polarities at both ends are slightly different or the same may beused. According to an example, as the horizontal alignment liquidcrystal compound, a compound having functional groups with thepolarities slightly different or the same at any one of R₇ to R₉ and anyone of R₂ to R₄ in Formula 1 may be used. Specifically, the horizontalalignment liquid crystal compound may be a compound in which any one ofR₇ to R₉ and any one of R₂ to R₄ is -U-Q-P or Formula 2, or two adjacentsubstituents of R₇ to R₉ and two adjacent substituents of R₂ to R₄ arelinked to each other to form a benzene substituted with -U-Q-P.

U may be —O—, —COO—, or —OCO—, Q may be an alkylene group or analkylidene group, and P may be an acryloyl group, a methacryloyl group,an acryloyloxy group, or a methacryloyloxy group.

Further, when any one of R₇ to R₉ and any one of R₂ to R₄ in Formula 1are selected as described above as the horizontal alignment liquidcrystal material, the other substituents may be hydrogen or an alkylgroup having 1 to 6 carbon atoms. However, the horizontal alignmentliquid crystal material is not limited thereto and may be appropriatelyselected depending on the use of the present invention.

In addition, as the vertical alignment liquid crystal material, acompound having a different polarity at both ends may be used. Accordingto an example, the vertical alignment liquid crystal material may be acompound in which any one of R₇ to R₉ in Formula 1 is -U-Q-P or Formula2, or two adjacent substituents of R₇ to R₉ are linked to each other toform a benzene substituted with -U-Q-P.

U may be —O—, —COO—, or —OCO—, Q may be an alkylene group or analkylidene group, and P may be an acryloyl group, a methacryloyl group,an acryloyloxy group, or a methacryloyloxy group.

Furthermore, when any one of R₇ to R₉ in Formula 1 is selected asdescribed above as the vertical alignment liquid crystal material, theother substituents may be hydrogen or an alkyl group. However, thevertical alignment liquid crystal material is not limited thereto, andany liquid crystal compound having a different polarity at both ends maybe selected without limitation.

The horizontal alignment liquid crystal film may have a normalwavelength dispersion characteristic, a flat wavelength dispersioncharacteristic, or a reverse wavelength dispersion characteristic. Inthe present specification, the normal wavelength dispersioncharacteristic may mean a characteristic that satisfies the followingEquation 1, the flat wavelength dispersion characteristic may mean acharacteristic that satisfies the following Equation 2, and the reversewavelength dispersion characteristic may mean a characteristic thatsatisfies the following Equation 3. According to an example of thepresent invention, wavelength dispersibility of the horizontal alignmentliquid crystal film may have a value of R (450)/R (550) of 0.8 to 1.2.

R(450)/R(550)>1   [Equation 1]

R(450)/R(550)≈1   [Equation 2]

R(450)/R(550)<1   [Equation 3]

In Equations 1 to 3, R (λ) may mean an in-plane retardation of theliquid crystal film with respect to the light having a wavelength of λnm. The in-plane retardation is a numerical value calculated as(Nx−Ny)×d. Here, Nx is a refractive index in the x-axis direction of theliquid crystal film, Ny is a refractive index in the y-axis direction ofthe liquid crystal film, and d is a thickness of the liquid crystalfilm. Here, the x-axis means any one direction on the plane of theliquid crystal film, and the y-axis means a direction on the planeperpendicular to the x-axis. In one example, the x-axis may be in adirection parallel to the slow axis of the liquid crystal film, and they-axis may be in a direction parallel to the fast axis of the liquidcrystal film. According to an example, the slow axis may be parallel tothe director of the liquid crystal material.

The horizontal alignment liquid crystal film may be manufactured byapplying a composition comprising the horizontal alignment liquidcrystal material on a substrate in which a horizontal alignment film isformed and polymerizing the composition.

In the present specification, when describing the application or coatingof B on A, this may mean that an appropriate surface treatment isperformed on A and B is applied or coated, unless otherwise specified.As the surface treatment, for example, a corona treatment, a plasmatreatment, and the like may be exemplified. The surface treatment mayimprove adhesion strength between the configuration A and theconfiguration B.

As the substrate, an inorganic film such as a glass film, a crystallineor non-crystalline silicon film, a quartz film or an indium tin oxide(ITO) film, or a plastic film, and the like may be used. As thesubstrate, an optically isotropic substrate, or an optically anisotropicsubstrate such as a retardation layer, and the like may be used.

As the plastic film, it is possible to use a substrate layer comprisingtriacetyl cellulose (TAC); a cyclo olefin copolymer (COP) such as anorbornene derivative; poly(methyl methacrylate) (PMMA); polycarbonate(PC); polyethylene (PE); polypropylene (PP); polyvinyl alcohol (PVA);diacetyl cellulose (DAC); polyacrylate (PAC); polyethersulfone (PES);polyether ether ketone (PEEK); polyphenylsulfone (PPS); polyetherimide(PEI); polyethylene naphthalate (PEN); polyethylene terephthalate (PET);polyimide (PI); polysulfone (PSF); polyarylate (PAR), or an amorphousfluororesin, and the like, but the plastic film is not limited thereto.

The first alignment film provided on the substrate comprise an alignmentmaterial and an acrylate, and a weight ratio of the alignment materialto the acrylate is 3:1 to 5:1. According to an example, the weight ratioof the alignment material to the acrylate may be 3:1 to 4:1. When thealignment material and the acrylate are not included within the weightratio range in the first alignment film, there is a problem in thatoptical characteristics of the polarizing plate deteriorate because thehaze value is high during the peeling of the substrate and the firstalignment film.

The haze value of the polarizing plate may be 0.1% to 1.0%, and may be0.1% to 0.5% according to an example. When the haze value is out of theabove range, optical characteristics deteriorate because thetransmittance of the degree of polarization is reduced, and when thehaze value satisfies the above range, there is an advantage in thatoptical characteristics do not deteriorate because the transmittance ofthe degree of polarization is not reduced.

The substrate may have a thickness of 40 μm to 100 μm. The firstalignment film may be a horizontal alignment film or a verticalalignment film, and the first alignment film comprises an alignmentmaterial and an acrylate as described above. In the presentspecification, the alignment material may mean a material which exhibitsliquid crystal alignability by irradiation with light, specifically,irradiation with polarized ultraviolet rays, and more specifically,irradiation with linearly polarized ultraviolet rays. The firstalignment film may be formed by applying a first alignment compositioncomprising the alignment material and the acrylate on the substrate andirradiating the first alignment composition with polarized ultravioletrays, specifically, linearly polarized ultraviolet rays. The alignmentmaterial may comprise at least one of polycinnamate, polyamide,polyimide, polyvinyl alcohol, and polyamic acid, but is not limitedthereto. More specifically, the alignment material may be4-benzyloxy-cinnamate-propyl-acrylate.

The acrylate included in the first alignment film may be amultifunctional acrylate, and the multifunctional acrylate may mean amaterial having two or more acrylate groups. As the multifunctionalacrylate, pentaerythritol triacrylate (PETA), dimethylol tricycle decanedimethacrylate (DCP-A), trimethylolpropane triacrylate (TMPTA),dipentaerythritol penta-/hexa-acrylate (DPHA), 1,6-hexanediol diacrylate(HDDA), and the like may be exemplified, but the multifunctionalacrylate is not limited thereto.

The first alignment composition may further comprise a solvent.

The polymerization of the first alignment composition may be performedby irradiating the first alignment composition with ultraviolet rays.The irradiation with ultraviolet rays may be performed at a temperatureof room temperature or 40° C. or less, and may be performed byirradiating the first alignment composition with ultraviolet rays at alight quantity of 200 mJ to 1,500 mJ for 1 second to 10 seconds.

The first alignment film may have a thickness of 0.1 μm to 3 μm.

The first liquid crystal film provided on the first alignment film maybe a horizontally or vertically alignment liquid crystal film, and maybe formed by applying a first liquid crystal composition comprising ahorizontal or vertical alignment liquid crystal material on a firstalignment film and irradiating the horizontal or vertical alignmentliquid crystal material with ultraviolet rays. The application of thefirst liquid crystal composition on the first alignment film may beperformed by a typical coating method. The coating method may beexemplified by roll coating, bar coating, comma coating, ink jet coatingor spin coating, and the like, and is not limited thereto.

The first liquid crystal composition may further comprise a solvent.

The polymerization of the liquid crystal material included in the firstliquid crystal composition may be performed by irradiating the firstliquid crystal composition with ultraviolet rays. The irradiation withultraviolet rays may be performed at a temperature of room temperatureor 40° C. or less, and may be performed by irradiating the first liquidcrystal composition with ultraviolet rays at a light quantity of 200 mJto 1,000 mJ for 1 second to 10 seconds.

The second alignment film provided on the first liquid crystal film maybe a vertical alignment film or horizontal alignment film, and comprisesa multifunctional acrylate. The multifunctional acrylate may mean amaterial having two or more acrylate groups. As the multifunctionalacrylate, pentaerythritol triacrylate (PETA), dimethylol tricycle decanedimethacrylate (DCP-A), trimethylolpropane triacrylate (TMPTA),dipentaerythritol penta-/hexa-acrylate (DPHA), and the like may be used.

When the second alignment film comprises a multifunctional acrylate, apolarizing plate having a low haze value may be manufactured, and thereis an advantage in that no unevenness occurs on the surface of themulti-layer liquid crystal film.

The second alignment film may be manufactured by applying a secondalignment composition comprising a multifunctional acrylate on the firstliquid crystal film and polymerizing the composition.

The second alignment composition may further comprise a photoinitiator.

The second alignment composition may further comprise a solvent.

Further, the second alignment composition may comprise 2 wt % to 15 wt %of a multifunctional acrylate, 0.2 wt % to 2 wt % of a photoinitiator,and 83 wt % to 97.5 wt % of a solvent. When the content of themultifunctional acrylate in the second alignment film composition isless than 2 wt %, the film strength is reduced so that scratches mayoccur during the additional coating, and when the content is more than15 wt %, the alignability of the liquid crystal may deteriorate.

As the photoinitiator, a photoinitiator widely-known in the art of thepresent invention may be used without limitation, and examples thereofcomprise a-amino ketones, acetophenones, benzoins, benzophenones,phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds,peroxides, 2,3-dialkyldione compounds, disulfide compounds, fluoroaminecompounds, aromatic sulfoniums, lophine dimers, onium salts, boratesalts, active esters, active halogens, inorganic complexes, coumarins,and the like.

The application of the second alignment film on the first liquid crystalfilm may be performed by a typical coating method. The coating methodmay be exemplified by roll coating, bar coating, comma coating, ink jetcoating or spin coating, and the like, and is not limited thereto.

The polymerization of the second alignment composition may be performedby irradiating the second alignment composition with ultraviolet rays.The irradiation with ultraviolet rays may be performed at a temperatureof room temperature or 40° C. or less, and may be performed byirradiating the second alignment composition with ultraviolet rays at alight quantity of 200 mJ to 1,500 mJ for 1 second to 10 seconds.

The second alignment film may have a thickness of 0.1 μm to 5 μm.

The second liquid crystal film may be formed by applying a second liquidcrystal composition comprising a vertical or horizontal alignment liquidcrystal material on the second alignment film and irradiating the secondliquid crystal composition with ultraviolet rays to polymerize thesecond liquid crystal composition. The application of the second liquidcrystal material on the second alignment film may be performed by atypical coating method. The coating method may be exemplified by rollcoating, bar coating, comma coating, ink jet coating or spin coating,and the like, and is not limited thereto.

The second liquid crystal composition may further comprise a solvent.

The solvent may be toluene, xylene, butyl cellosolve, diethylene glycoldimethyl ether, and the like, but is not limited thereto.

The polymerization of the liquid crystal material included in the secondalignment film composition may be performed by irradiating the secondalignment film composition with ultraviolet rays. The irradiation withultraviolet rays may be performed at a temperature of room temperatureor 50° C. or less, and may be performed by irradiating the secondalignment film composition with ultraviolet rays at a light quantity of300 mJ to 1,500 mJ for 1 second to 10 seconds.

The thickness of the first liquid crystal film or second liquid crystalfilm may be appropriately adjusted according to the use of themulti-layer liquid crystal film. According to an example, the firstliquid crystal film and the second liquid crystal film may have athickness of 1 μm to 10 μm, respectively, and according to anotherexample, the first liquid crystal film and the second liquid crystalfilm may have a thickness of 1 μm to 5 μm, respectively, but thethickness is not limited thereto.

The multi-layer liquid crystal film of the present invention may notinclude an adhesive agent between the first liquid crystal film and thesecond alignment film, or between the second liquid crystal film and thesecond alignment film. The multi-layer liquid crystal film has anadvantage in that the thickness may be thinned as compared to amulti-layer liquid crystal film stacked through an adhesive agent.

According to an exemplary embodiment of the present invention, asillustrated in FIG. 1, the multi-layer liquid crystal film may bestacked in the order of a substrate 1, a first alignment film 2, a firstliquid crystal film 3, a second alignment film 4, and a second liquidcrystal film 5, and a structure of the multi-layer liquid crystal filmaccording to this example of the present invention is also illustratedin FIG. 1.

In the multi-layer liquid crystal film according to an exemplaryembodiment of the present invention, the first alignment film may be avertical alignment film, the first liquid crystal film may be a verticalalignment liquid crystal film, the second alignment film may be ahorizontal alignment film, and the second liquid crystal film may be ahorizontal alignment liquid crystal film.

In the multi-layer liquid crystal film according to an exemplaryembodiment of the present invention, the first alignment film may be ahorizontal alignment film, the first liquid crystal film may be ahorizontal alignment liquid crystal film, the second alignment film maybe a vertical alignment film, and the second liquid crystal film may bea vertical alignment liquid crystal film.

The polarizing plate according to an exemplary embodiment of the presentinvention comprises: a polarizer; and the above-described multi-layerliquid crystal film provided on at least one surface of the polarizer,in which the second liquid crystal film is disposed adjacent to thepolarizer.

As illustrated in FIG. 4, the polarizing plate according to anotherexemplary embodiment comprises: a polarizer 6; a first alignment film 2provided on at least one surface of the polarizer; a first liquidcrystal film 3 provided on the first alignment film; a second alignmentfilm 4 provided on the first liquid crystal film; and a second liquidcrystal film 5 provided on the second alignment film, in which the firstalignment film comprises an alignment material and an acrylate, and aweight ratio of the alignment material to the acrylate is 3:1 to 5:1.

The content described on the multi-layer liquid crystal film may beapplied equally to the first alignment film, the first liquid crystalfilm, the second alignment film, and the second liquid crystal film,unless otherwise specified. The polarizing plate as described above maybe manufactured by peeling off a substrate from the above-describedpolarizer; and a polarizing plate in which a second liquid crystal filmof the above-described multi-layer liquid crystal film is disposedadjacent to the polarizer on at least one surface of the polarizer.

As illustrated in FIGS. 1 and 2, an exemplary embodiment of the presentinvention provides a method for manufacturing a polarizing plate, themethod comprising: forming a first alignment film 2 on a substrate 1 bycoating the substrate 1 with a first alignment film compositioncomprising an alignment material and an acrylate, in which a weightratio of the alignment material to the acrylate is 3:1 to 5:1; forming afirst liquid crystal film 3 on the first alignment film 2; forming asecond alignment film 4 on the first liquid crystal film 3; and forminga second liquid crystal film 5 on the second alignment film.

Another exemplary embodiment of the present invention provides a methodfor manufacturing a polarizing plate, the method comprising: forming afirst alignment film 2 on a substrate 1 by coating the substrate 1 witha first alignment composition comprising an alignment material and anacrylate, in which a weight ratio of the alignment material to theacrylate is 3:1 to 5:1; forming a first liquid crystal film 3 on thefirst alignment film 2; forming a second alignment film 4 on the firstliquid crystal film 3; forming a second liquid crystal film 5 on thesecond alignment film; laminating the second liquid crystal film 5 to apolarizer 6; and peeling off the substrate 1 (FIG. 3). The contentdescribed on the multi-layer liquid crystal film may be applied equallyto the substrate 1, the first alignment film 2, the first liquid crystalfilm 3, the second alignment film 4, and the second liquid crystal film5, unless otherwise specified.

In the method for manufacturing a polarizing plate, thinning of thepolarizing plate may be achieved by peeling off of the substrate 1.

A peeling strength between the substrate and the first alignment filmmay be 0.5 N or less.

Further, by providing an alignment material and an acrylate at a weightratio of 3:1 to 5:1 in a first alignment film in the method formanufacturing a polarizing plate, there are advantages in that when asubstrate 1 is peeled off by adjusting the peeling strength between thesubstrate and the first alignment film to 0.5 N or less, opticalcharacteristics of the polarizing plate do not deteriorate due to a lowhaze value, and a problem in that transfer is not performed during asubsequent transfer process.

A method for manufacturing a polarizing plate according to the presentinvention is illustrated in FIGS. 2 and 3, FIG. 2 illustrates forming afirst alignment film 2 on a substrate 1 by coating the substrate 1 witha first alignment composition comprising an alignment material and anacrylate, in which a weight ratio of the alignment material to theacrylate is 3:1 to 5:1; forming a first liquid crystal film 3 on thefirst alignment film 2; forming a second alignment film 4 on the firstliquid crystal film 3; and forming a second liquid crystal film 5 on thesecond alignment film, and FIG. 3 illustrates laminating the secondliquid crystal film 5 to a polarizer 6; and peeling off the substrate 1.

In the method for manufacturing a polarizing plate of the presentinvention, an adhesive agent may not be included between the firstliquid crystal film and the second alignment film, or between the secondliquid crystal film and the second alignment film. The thus-manufacturedmulti-layer liquid crystal film has an advantage in that the thicknessmay be reduced as compared to a multi-layer liquid crystal film stackedthrough an adhesive agent.

As the polarizer, those known in the art may be used. For example, it ispossible to use a polarizer in which iodine or a dichroic dye isadsorbed and alignment to a polyvinyl alcohol-based (hereinafter,referred to as PVA) polymer film.

The polarizer and the second liquid crystal film may be laminated toeach other by using a bonding or adhesive agent. As the bonding oradhesive agent, those known in the art may be used. For example, apressure-sensitive adhesive (PSA) or a UV adhesive (UVA) may be used.

When a multi-layer liquid crystal film, in which a first alignment filmcomprising an alignment material and an acrylate in which a weight ratioof the alignment material to the acrylate is 3:1 to 5:1; a first liquidcrystal film provided on the first alignment film; a second alignmentfilm provided on the first liquid crystal film; and a second liquidcrystal film provided on the second alignment film are stacked in thisorder on one surface of the polarizer, is formed, an additional film maybe provided on the other surface of the polarizer.

As the additional film, those known in the art may be used, and it ispossible to use, for example, a triacetate cellulose (TAC) film, apolynorbornene-based film manufactured by an acrylic film ring openingmetathesis polymerization (ROMP), a ring opening metathesispolymerization followed by hydrogenation (ROMP) polymer film obtained bysubjecting a ring opening polymerized cyclic olefin-based polymer tohydrogenation again, a polyester film, a polynorbornene-based filmmanufactured by addition polymerization, and the like. Besides, a filmmanufactured of a transparent polymer material may be used as aprotective film, and the like, but is not limited thereto.

An exemplary embodiment of the present invention provides a liquidcrystal display device comprising the above-described polarizing plate.In the liquid crystal display device, the polarizer or multi-layerliquid crystal film of the above-described polarizing plate may bedisposed close to the liquid crystal panel. The substrate of themulti-layer liquid crystal film may be peeled off before or after theabove-described polarizer is attached to the liquid crystal panel. Thepolarizing plate may be attached to the liquid crystal panel through apressure-sensitive adhesive (PSA), and as the pressure-sensitiveadhesive, those known in the art may be used.

The liquid crystal display device may comprise a backlight unit. Thebacklight unit may comprise a light source, a light guide plate, and anoptical film such as a light-collecting film or a brightness enhancementfilm, and may have a configuration known in the art. Furthermore, in theliquid crystal display device, the above-described polarizing plate maybe used for an upper polarizing plate or a lower polarizing plate.

EXAMPLES

Hereinafter, exemplary embodiments of the present application will beexemplified through Examples. The following Examples are provided forexemplifying the invention of the present application, and are notintended to limit the present invention by the Examples.

Preparation Examples Preparation Example 1

After corona treatment on the surface of a plastic substrate (NormalTAC) (thickness 40 μm), a mixture solution in which an alignmentmaterial (4-benzyloxy-cinnamate-propyl-acrylate) and 1,6-hexanedioldiacrylate (HDDA) were mixed at a weight ratio of 3:1 was appliedthereon, and irradiated with ultraviolet rays to form a verticalalignment film. After corona treatment on the surface of the verticalalignment film, a vertically alignment liquid crystal composition (avertical alignment liquid crystal material (RMM460, Merck) was dilutedwith toluene and diethylene glycol dimethyl ether solvents to aconcentration of 23%) was applied thereon, and irradiated withultraviolet rays at a light quantity of 1,000 mJ to form a verticalalignment liquid crystal film having a thickness of 1.5 μm, therebymanufacturing a liquid crystal film.

After corona treatment on the surface of the vertical alignment liquidcrystal film, a horizontal alignment film composition (comprising 5 wt %of a multifunctional acrylate pentaerythritol triacrylate (PETA), 0.5 wt% of a photoinitiator (Irg184, Ciba), and the balance solvent) wasapplied thereon and irradiated with ultraviolet rays to form ahorizontal alignment film. After corona treatment on the surface of thehorizontal alignment film, a horizontal alignment liquid crystalcomposition (a horizontally alignment liquid crystal material (RMM1290,Merck) was diluted with toluene and butyl cellosolve solvents to aconcentration of 25 wt %) was applied thereon, and irradiated withultraviolet rays at a light quantity of 700 mJ to polymerize thehorizontal alignment liquid crystal composition, thereby forming ahorizontal alignment liquid crystal film having a thickness of 1.5 μm.The liquid crystal film had a total thickness of 43 μm.

Preparation Example 2

After corona treatment on the surface of a plastic substrate (NormalTAC) (thickness 40 μm), a mixture solution in which an alignmentmaterial (4-benzyloxy-cinnamate-propyl-acrylate) and 1,6-hexanedioldiacrylate (HDDA) were mixed at a weight ratio of 6:1 was appliedthereon, and irradiated with ultraviolet rays to form a verticalalignment film. A liquid crystal film was manufactured in the samemanner as in Preparation Example 1, except that the manufacturedvertical alignment film was used.

Preparation Example 3

After corona treatment on the surface of a plastic substrate (NormalTAC) (thickness 40 μm), a mixture solution in which an alignmentmaterial (4-benzyloxy-cinnamate-propyl-acrylate) and 1,6-hexanedioldiacrylate (HDDA) were mixed at a weight ratio of 2.5:1 was appliedthereon, and irradiated with ultraviolet rays to form a verticalalignment film. A liquid crystal film was manufactured in the samemanner as in Preparation Example 1, except that the manufacturedvertical alignment film was used.

Preparation Example 4

After corona treatment on the surface of a plastic substrate (NormalTAC) (thickness 40 μm), a mixture solution in which an alignmentmaterial (4-benzyloxy-cinnamate-propyl-acrylate) and 1,6-hexanedioldiacrylate (HDDA) were mixed at a weight ratio of 2:1 was appliedthereon, and irradiated with ultraviolet rays to form a verticalalignment film. A liquid crystal film was manufactured in the samemanner as in Preparation Example 1, except that the manufacturedvertical alignment film was used.

Preparation Example 5

After corona treatment on the surface of a plastic substrate (NormalTAC) (thickness 40 μm), a mixture solution of triacrylate and butylacrylate was applied thereon, and irradiated with ultraviolet rays toform a vertical alignment film. A liquid crystal film was manufacturedin the same manner as in Preparation Example 1, except that themanufactured vertical alignment film was used.

Preparation Example 6

After corona treatment on the surface of a plastic substrate (NormalTAC) (thickness 40 μm), a mixture solution of poly(methyl methacrylate)(PMMA) and pentaerythritol triacrylate (PETA) was applied thereon, andirradiated with ultraviolet rays to form a vertical alignment film. Aliquid crystal film was manufactured in the same manner as inPreparation Example 1, except that the manufactured vertical alignmentfilm was used.

Preparation Example 7

After corona treatment on the surface of a plastic substrate (NormalTAC) (thickness 40 μm), a pentaerythritol triacrylate (PETA) mixturesolution was applied thereon, and irradiated with ultraviolet rays toform a vertical alignment film. A liquid crystal film was manufacturedin the same manner as in Preparation Example 1, except that themanufactured vertical alignment film was used.

Preparation Example 8

After corona treatment on the surface of a plastic substrate (NormalTAC) (thickness 40 μm), an alignment material(4-benzyloxy-cinnamate-propyl-acrylate) mixture solution was appliedthereon, and irradiated with ultraviolet rays to form a verticalalignment film. A liquid crystal film was manufactured in the samemanner as in Preparation Example 1, except that the manufacturedvertical alignment film was used.

Experimental Example 1 Comparative Example 1-1

A multi-layer liquid crystal film was manufactured in the same manner asin Preparation Example 1, except that a horizontal alignment liquidcrystal film was formed immediately on a vertical alignment liquidcrystal film without forming a horizontal alignment film in PreparationExample 1.

Evaluation of Coatability

After the polarizing plates were orthogonal to each other, thecoatability in a large area was compared between the polarizing plates,and the magnitude of dewetting was evaluated using a polarizationmicroscope (NIKON, ECLIPSE LV100 POL). As a result of the coatabilityevaluation, it can be confirmed that the coatability is improved becausethe dewetting in Preparation Example 1 is decreased as compared to thatin Comparative Example 1-1.

Experimental Example 2 Example 1

After corona treatment on the horizontal alignment liquid crystal film(the second liquid crystal film) of the liquid crystal film manufacturedin Preparation Example 1, the horizontal alignment liquid crystal filmwas laminated to a polarizing plate by using an acrylate-based adhesiveagent. After the lamination, a plastic substrate of the liquid crystalfilm was peeled off.

Comparative Example 1

A polarizing plate was manufactured in the same manner as in Example 1,except that the liquid crystal film manufactured in Preparation Example2 was used instead of the liquid crystal film manufactured inPreparation Example 1, which was used in Example 1.

Comparative Example 2

A polarizing plate was manufactured in the same manner as in Example 1,except that the liquid crystal film manufactured in Preparation Example3 was used instead of the liquid crystal film manufactured inPreparation Example 1, which was used in Example 1.

Comparative Example 3

A polarizing plate was manufactured in the same manner as in Example 1,except that the liquid crystal film manufactured in Preparation Example4 was used instead of the liquid crystal film manufactured inPreparation Example 1, which was used in Example 1.

Comparative Example 4

A polarizing plate was manufactured in the same manner as in Example 1,except that the liquid crystal film manufactured in Preparation Example5 was used instead of the liquid crystal film manufactured inPreparation Example 1, which was used in Example 1.

Comparative Example 5

A polarizing plate was manufactured in the same manner as in Example 1,except that the liquid crystal film manufactured in Preparation Example6 was used instead of the liquid crystal film manufactured inPreparation Example 1, which was used in Example 1.

Comparative Example 6

A polarizing plate was manufactured in the same manner as in Example 1,except that the liquid crystal film manufactured in Preparation Example7 was used instead of the liquid crystal film manufactured inPreparation Example 1, which was used in Example 1.

Comparative Example 7

A polarizing plate was manufactured in the same manner as in Example 1,except that the liquid crystal film manufactured in Preparation Example8 was used instead of the liquid crystal film manufactured inPreparation Example 1, which was used in Example 1.

Measurement of Peeling Strength

A peeling strength at the interface was measured by using a textureanalyzer (TA-XTplus manufactured by Stable Micro System Corporation)between the substrate film and the liquid crystal layer in themanufactured liquid crystal film. In this case, a test method inaccordance with ASTM D 6862 was used.

Measurement of Haze Values

The manufactured multi-layer liquid crystal film was measured by a hazemeter (HM-150 manufactured by Murakami Color Research Laboratory Co.,Ltd.).

Measurement of Ts (%), Tc (%), and DOP (%)

After the polarizing plates manufactured by the Examples and theComparative Examples were cut into a size of 40 mm×40 mm and the testspecimens were fixed to a measurement holder, initial opticalproperties, that is, a single body transmittance (Ts), a crossedtransmittance (Tc), and a degree of polarization (DOP, %) were measuredby using a UV-visible light spectrometer (V-7100, manufactured by JASCOCorp.). The single body transmittance (Ts) is a value measured for onepolarizing plate, and the crossed transmittance (Tc) was measured afterthe two cut polarizing plates are orthogonal to each other such that theabsorption axes thereof become 90 degrees, and the single bodytransmittance (Ts) and the crossed transmittance (Tc) are shown inTable 1. The degree of polarization (DOP, %) is defined as the followingequation by the parallel transmittance (Tp) obtained when two polarizingplates are disposed in a state in which the absorption axes thereof areparallel to each other and the crossed transmittance (Tc) obtained afterthe two polarizing plates were orthogonal to each other so as to makethe absorption axes form an angle of 90 degrees.

DOP=[(Tp−Tc)/(Tp+Tc)]×½

The haze, Ts, Tc, and DOP of each of Example 1 and Comparative Examples1 to 7 were measured, and the results thereof are shown in the followingTable 1.

TABLE 1 Peeling strength (N) Haze (%) Ts (%) Tc (%) DOP (%) Example 10.1 0.3 42.29 0.0019 99.9947 Comparative  0.05 5.6 39.98 0.0057 99.9687Example 1 (Occurrence of scratches) Comparative 1.5 1.2 41.92 0.002799.9900 Example 2 Comparative 2.2 2.0 41.85 0.0032 99.9868 Example 3Comparative 1.2 4.2 41.24 0.0035 99.9859 Example 4 Comparative 1.0 2.741.78 0.0029 99.9916 Example 5 Comparative Not peeled — — — — Example 6off Comparative 0.2 4.8 40.13 0.0043 99.9724 Example 7 (Occurrence ofscratches)

From Table 1, it can be confirmed that Example 1 of the presentapplication has a lower haze value and better optical properties of thepolarizing plate than those in Comparative Examples 2 to 5, and it canbe confirmed that in Comparative Examples 1 and 7, scratches occur atthe time of peeling off the substrate, and as a result, the haze valueof the polarizing plate is increased to a very high level and opticalproperties deteriorate. Furthermore, it can be confirmed that inComparative Example 6, a thinned polarizing plate cannot be obtainedbecause the substrate is not peeled off.

1. A multi-layer liquid crystal film comprising: a substrate; a firstalignment film provided on the substrate; a first liquid crystal filmprovided on the first alignment film; a second alignment film providedon the first liquid crystal film; and a second liquid crystal filmprovided on the second alignment film, wherein the first alignment filmcomprises an alignment material and an acrylate, and a weight ratio ofthe orientation material to the acrylate is 3:1 to 5:1.
 2. Themulti-layer liquid crystal film of claim 1, wherein the first alignmentfilm is a horizontally alignment film, the first liquid crystal film isa horizontally alignment liquid crystal film, the second alignment filmis a vertically alignment film, and the second liquid crystal film is avertical alignment liquid crystal film.
 3. The multi-layer liquidcrystal film of claim 1, wherein the first alignment film is avertically alignment film, the first liquid crystal film is a verticallyalignment liquid crystal film, the second alignment film is ahorizontally alignment film, and the second liquid crystal film is ahorizontally alignment liquid crystal film.
 4. The multi-layer liquidcrystal film of claim 1, wherein the second alignment film comprises amultifunctional acrylate.
 5. The multi-layer liquid crystal film ofclaim 1, wherein a peeling strength between the substrate and the firstalignment film is 0.5 N or less.
 6. A polarizing plate comprising: apolarizer; and the multi-layer liquid crystal film of claim 1 providedon at least one surface of the polarizer, wherein the second liquidcrystal film is disposed adjacent to the polarizer.
 7. A polarizingplate comprising: a polarizer; a first alignment film provided on atleast one surface of the polarizer; a first liquid crystal film providedon the first alignment film; a second alignment film provided on thefirst liquid crystal film; and a second liquid crystal film provided onthe second alignment film, wherein the first alignment film comprises analignment material and an acrylate, and a weight ratio of theorientation material to the acrylate is 3:1 to 5:1.
 8. A method formanufacturing a polarizing plate, the method comprising: forming a firstalignment film on a substrate by coating the substrate with a firstalignment composition comprising an alignment material and an acrylate,wherein a weight ratio of the alignment material to the acrylate is 3:1to 5:1; forming a first liquid crystal film on the first alignment film;forming a second alignment film on the first liquid crystal film; andforming a second liquid crystal film on the second alignment film. 9.The method of claim 8, comprising: laminating the second liquid crystalfilm to a polarizer after the forming of the second liquid crystal filmon the second alignment film; and peeling off the substrate.
 10. Themethod of claim 8, wherein the forming of the second alignment filmforms the second alignment film by coating the second alignment filmwith a second alignment composition comprising a multifunctionalacrylate.
 11. The method of claim 10, wherein the second alignment filmcomposition comprises 2 wt % to 15 wt % of a multifunctional acrylate,0.2 wt % to 2 wt % of a photoinitiator, and 83 wt % to 97.5 wt % of asolvent.
 12. The method of claim 8, wherein the first alignment film isa horizontally alignment film, the first liquid crystal film is ahorizontal alignment liquid crystal film, the second alignment film is avertically alignment film, and the second liquid crystal film is avertically alignment liquid crystal film.
 13. The method of claim 8,wherein the first alignment film is a vertically alignment film, thefirst liquid crystal film is a vertical alignment liquid crystal film,the second alignment film is a horizontally alignment film, and thesecond liquid crystal film is a horizontally alignment liquid crystalfilm.
 14. The method of claim 9, wherein a peeling strength between thesubstrate and the first alignment film is 0.5 N or less.
 15. The methodof claim 8, wherein an adhesive agent is not formed between the firstliquid crystal film and the second alignment film, or between the secondliquid crystal film and the second alignment film.